Process for dyeing polyolefinic materials



United States Patent C) 3,316,054 PROCESS FOR DYElNG POLYDLEFINIC MATERIALS Yoshio Tsnnoda, Tokyo, Torn Taneda, Ibaragi-shi, Kiyoshi Akamatsu, Toyonaka-shi, Toshio Okamoto, Kyoto, and Kenichi Matsni, Takatsuki-shi, Japan, assignors to Asahi Kasel Kogyo Kabushiki Kaisha, Osaka, Japan, a corporation of Japan N Drawing. Filed Mar. 11, 1964, Ser. No. 351,211 Claims priority, application Japan, Dec. 23, 1960, 35/49,776 5 Claims. (Cl. 8-100) This application is a continuationin-part of our earlier application, Ser. No. 139,061, filed Sept, 19, 1961.

This invention relates to processes for improving the dyeability of articles made of polyolefins.

It is well known that the poor dyeing characteristics of polyolefin constitutes a problem which is important in spite of the many other excellent properties of this material. It is also known that many attempts have been made to improve the dyeability of polyolefins.

These attempts include admixing polyolefins with polyethylene imines, polyamides, polyurethanes, polyureas, epoxy resins or polyvinyl resins which have an aflinity for acid dyes, substituting amino groups for chlorine in chlorinated polyolefin articles and grafting onto polyolefin articles such compounds as 2-methyl-5-viny1 pyridine and so on.

However, polyolefin is not improved by these known methods to an extent such as to be suitable for dyeing by all kinds of acid dyes. Further, polyolefin articles, which are improved to an extent such that their excellent physical properties are not damaged, cannot be dyed well with an efiicient exhaustion of dye in the associated dyebath and, moreover, cannot be dyed to deep or black shades.

We have now found, according to the invention, that the dyeability of polyolefin articles can be improved remarkably by employing monocyclic aromatic carboxylic acids including benzoic acid, salicyclic acid, gallic acid, cinnamic acid, phthalic acid and their derivatives such as methyl salicylic acid, nitrobenzoic acid, nitrosobenzoic acid, nitrophthalic acid, chlorobenzoic acid, anthranilic acid, dihydroxyphthalic acid, hydroxyphthalic acid and sulfosalicyclic acid.

It is an object of the process for remarkably olefin articles by the acids.

It is another object of the invention to provide improved process for remarkably improving the dyeing efiiciency of said articles by employing said compounds in a dye bath.

It is a further object of the invention to provide an improved process for dyeing polyolefin articles without harming the other physical properties of this material.

According to this invention, the acid treatment and the dyeing may be efiected simultaneously, by the use of a dyeing bath containing the aromatic carboxylic acid, or alternatively an article may be pretreated with the aromatic carboxylic acid and then dyed to the desired color. In this case dyeing may be effected immediately after the pretreatment with the aromatic carboxylic acid, or after a considerable length of time has elapsed. The conditions for the aromatic carhoxylic acid treatment may vary depending upon the concentration of the acid, the temperature and duration of the treatment and the present invention to provide a improving the dyeability of polyuse of said aromatic carboxylic bath ratio used. Usually, however, the aromatic carboxylic acid should be used in an amount of at least 1% based on the weight of the article to be dyed. The temperature employed may, generally speaking, be with in the range of from room temperature up to 150 C. On the commercial scale it is possible to subject the shaped polyolefin article to immersion at a relatively low temperature for a considerable time, followed by dyeing in another processing plant (e.g., a dyeing factory). It is also possible to carry out the dyeing and aromatic carboxylic acid treatment in one operation by the use of a dyeing bath containing the said acid at a temperature of about C.

Polyolefins to be used in this invention are modified by the addition thereto 1 to 20% by weight of a material having a melting point between 100 and 300 C. and having the following general formula:

wherein R and R are members selected from the group consisting of alkylene, phenylene, cycloalkylene, pyridyl, and naphthyl radicals, the alkylene radical being represented by the formula (CH wherein m is a number between 2 and 10; X and X are members selected from the group consisting of hydrogen, alkyl, alkenyl, phenyl, naphthyl, amino, benzalamino, formalamino, acetamino, carbamylamino, pyrrolyl and pyridyl radicals, the alkyl radical having from 1 to 18 carbon atoms and being linear or branched, the alkenyl radical having from 2 to 18 carbon atoms; Z and Z are selected from the group consisting of carboxyl and hydrazide radicals; and n is a number greater than one.

Examples of the said material to be advantageously used in this invention are next given for the sake of illustration:

N-N NHN all (ii; h

N/ N 11111; 2n I i 2n N-N N R t & it L I TH I I 11 It is to be realized that in the foregoing examples, the end group of the particular material utilized therein is either carboxyl (COOH), or the hydrazide (CONHNH (b) If the carboxyl radical of the end is linked with acetamide (CH CONH and amide will be joined as follows:

V (2) Where there is used monocarboxylhydrazide:

(a) If the hydrazide radical of the end is linked with lauric acid hydrazide [CH (CH CONHNHz], aminotriazole will be joined, resulting in the formation of 3-substituted 4-arnino-triazole as follows:

4 (b) If the carboxyl radical of the end is linked with acetohydrazide (CI-I CONHNH oxadiazole will be formed as follows:

[POlymGr COOH CIIQCONIINHZ l il [Polymer% C-CH The polyolefins having been mixed with the abovedescribed additive material can be as easily shaped or processed as ordinarily polyolefins, without suffering from discoloration or degradation and decrease in processability.

The present invention provides numerous advantages. Firstly, the present invention enables an efficient dyeing of polyolefin articles and is of value from the viewpoint of economics. Secondly, the invention enables the use of polyolefin which is less modified than with conventional techniques. Thirdly, the invention enables the use of all kinds of commercially available acid dyes, especially acid dyes and disperse dyes for the dyeing of polyolefin articles and further yields durable products which may be dyed in all kinds of shade.

We are aware of the Meunier Pat. No. 2,628,152,, wherein it is recommended to dye modified polyacrylonitrile staple fabric with an acid dye in the presence of benzoic acid or salicylic acid. The difierences between said patent and our invention are important. Meunier merely discloses a levelling effect by the use of benzoic acid or salicylic acid and is not concerned with improving dyeability of a shaped polyolefinic material which has. added thereto a polytriazole with the use of aromatic carboxylic acids for adsorbability of dyestuffs.

The following examples will serve to illustrate the present invention in detail.

The 118 Standards, 5th class, consists of two tests, a washing test and a rubbing test, and is carried out as follows:

(i) Washing test.The test is carried out by attaching a white silk cloth and a white cotton cloth to a test cloth, immersing the test cloth for 30 minutes in an aqueous solution containing 0.5% of soap (liquor ratio=50:1), maintained at 50i1 C., subjecting the test cloth to water-washing and dehydration, and then drying at temperatures of 70-75 C.

(ii) Rubbing test.This test is conducted by attaching a test cloth to one end of a glass rod with 1.5 cm. diameter and then rubbing the test cloth against a white cotton cloth while sliding the test cloth back and forth 10 times between a distance of 10 cm.

Evaluation: 118, 5th class:

(1) No change in original color,

(2) No staining of the White cloths,

(3) No bleeding.

Example 1 A mixture of 5 parts by Weight sebacic acid dihydrazide and 1 part by weight hydrazine hydrate was subjected to reaction under normal pressure in an atmosphere of nitrogen and the resulting condensation polymer was found on chemical analysis to contain 20% nitrogen. It was identified as poly(octamethylene triazole) (12:5) by infrared absorption spectrum. The melting point of the product was 180 C. It was mixed, in an amount of 5% by weight, with powdered polypropylene resin having an average molecular weight of 200,000, and the resulting mixture was subjected to melt spinning by extrusion at 250 C. to produce yarn comprising rnonofilaments of 6 deniers. The yarn was immersed in a solution containing salicylic acid at a concentration of g./l. at 60 C., was left to stand overnight, was washed with water and then dried. Then it was dyed to a brilliant red color with 3% Benzyl Fast Yellow GR (C.I. Acid Yellow 40, 18,950) at a bath ratio of 50 and a temperature of 100 C. The dyed material passed the HS, 5th class, in its resistance to abrasion and laundering.

Example 2 To low pressure polyethylene pellet having an average molecular weight of 150,000, was added 5% by weight poly (tetramethylene N-benzal-aminotriazole) (11:3), obtained by reacting adipic acid dihydrazide-condensation polymer with benzaldehyde. The mixture was passed into a pelletizer at 240 C. to produce pellets which were then melt-spun by means of an extruder at 240 C. to produce yarn comprising monofilaments of 10 deniers. The yarn so produced was dyed to a deep yellow color by using a dyeing bath of 3% Dispersol Fast Yellow G (C.I. Disperse Yellow 3, 11,855) containing salicylic acid at a concentration of 20 g./l., at a bath ratio of 50 and a temperature of 100 C. The dyed material had good resistance to both abrasion and laundering, high enough to pass the 118 Standards, 5th class.

Example 3 The same yarn as was used in Example 2 was dyed to a deep blue color with 3% Benzyl Blue RBF (C.I. Acid Blue 15, 42,645) in a 10 g./l. terephthalic acid-containing bath at a bath ratio of 20 and a temperature of 100 C. The dyed material passed the 118 Standards, 5th class, in its resistance to abrasion and laundering.

Example 4 3% by weight poly(phenylene methyltriazole) (11:1), obtained by reacting terephthalic acid dihydrazide-condensed polymer with sodium methylate and methyl iodide, was added to polypropylene resin pellet having an average molecular weight of 100,000 and the resulting mixture was passed through an extruder to produce a mixed pellet. This was then extruded at 240 C. to produce yarn comprising monofilaments of 5 deniers. The yarn was dyed with 3% Coomassie Fast Scarlet B (C.I. Acid Red 111, 23,265) in a 20 g./l. gallic acid-containing dyeing bath (the bath ratio was 30 and the temperature 100 C.). The dyed material passed the HS Standards, 5th class, in its resistance to abrasion and laundering.

Example 5 To low pressure polyethylene resin having an average molecular weight of 150,000, 5% by weight of a 1,4- cyclohexyl dicarboxylic acid dihydrazide condensation polymer (11:4) in which the amino group of the aminotriazole portion of the polymer has been converted into hydrogen by reaction with nitrous acid was added. The mixture was melt-spun to produce yarn of 10 denier monofilaments. The yarn was treated with a solution containing salicylic acid at a concentration of 20 g./l. at 100 C. for thirty minutes and was then washed with water. The thus treated yarn was dyed to a brilliant 6 yellow orange color by using 5% Celliton Fast Yellow 5R (C.I. Disperse Yellow 7, 26,090) at a bath ratio of 50 and at a temperature of C. The dyed material passed the HS Standards, 5th class, in its resistance to abrasion and laundering.

Example 6 To low pressure polyethylene pellet having an average molecular weight of 150,000, was added 5% by weight of the reaction product of adipic acid dihydrazide condensation polymer (11:75) with sodium methylate and methyl iodide. Additive-mixed pellet was formed by means of a pelletizer at 240 C., and then 10 denier yarn was obtained therefrom by a melt spinning process. The yarn was dyed to a brilliant blue color with 3% Xylene Brilliant Cyanine 6B (C.I. Acid Blue 83, 42,660) in a 15 g./l. benzoic acid-containing bath of bath ratio 30 at a temperature of 100 C. for one hour. The fastness of the dyed material was found to be 5th class as determined by JIS Standards.

Example 7 3% by weight poly(octarnethylene aminotriazole) (n=2) and 2% by weight poly(tetramethylene benzalamino-triazole) (11:5) were intimately mixed with polyethylene resin powder having an average molecular weight of 120,000. The resulting mixture was extruded and shaped to fibre form, thereby producing yarn of 15 deniermonofilamcnts. The yarn was dyed to a beautiful deep purple color by using a dyeing bath of bath ratio 50 at 100 C., the bath containing 5% Benzyl Violet 3B (C.I. Acid Violet 17, 42,650) and 20%, based on the weight of the yarn, cinnamic acid. The dyed material passed the ITS Standards 5th class in fastness.

Example 8 To polypropylene resin powder having an average molecular weight of 100,000, was added 3% by weight poly (phenylene acetaminotriazole) (11:1). The resulting mixture was extruded and spun to produce yarn of 10 denier monofilament. The yarn was treated in a bath containing benzoic acid at a concentration of 20 g./l., at 100 C. for one hour, and was then dyed to a beautiful red color with Rose Bengale (C.I. Acid Red 94, 45,440) at a bath ratio of 50 and at a temperature of 100 C.

Example 9 To polybutene-l resin pellet having an average molecular weight of 150,000, was added polytjtetramethylene triazole) (11:18), obtained by the condensation polymerisation of adipic acid dihydrazide with hydrazine hydrate. A mixed pellet was formed, by means of a pelletizer, and it was then passed into an extruder to produce spun yarn of 10 denier monofilaments. The yarn was dyed to a beautiful deep blue color by using 5% Benzyl Blue RBF (C.I. Acid Blue 15, 42,645) in a dyeing bath containing 5 g./l. benzoic acid at a bath ratio of 30 at 100 C. The fastness of the dyed material was good enough to pass the I IS Standards, 5th class.

Example 10 By the condensation polymerization of sebacic acid dihydrazide, a triazole-aminotriazole condensation polymerisation product (It-=10), having a nitrogen content ott 25%, was prepared. 5% by weight of the above product was added to polypropylene resin powder having an average molecular weight of 150,000. The resulting mixture was subjected to melt spinning by means of a 250 C., and hot extruder to produce yarn of 6 denier monofilaments. The yarn was treated with a solution of 5 g./l. chlorobenzoic acid at 100 C. for one hour and was then dyed to a deep yellow color with 3% Chrysophenine NS conc. (C.I. Direct Yellow 12, 24,895) at a bath ratio of 50 for one hour. The fastness was found to be JIS Standards, 5th class.

of 30, and at a temperature of 100 C. The fastness of the dyed material was found to be th class on the 118 Standards.

Example 12 To polyethylene resin pellet having an average molecular weight of 100,000, was added 3% by weight of a mixed adipic acid dihydrazide-sebacic acid dihydrazide condensation polymer having a melting point of 210 C. The resulting intimate mixture was pelletized at 250 C. and the pellet was then passed to an extruder at 260 C. to produce yarn of 6 denier monofilaments. The yarn was dyed to a beautiful purple color by using 5% Celanthrene Violet CB (C.I. Disperse Violet 4, 61,105) in a g./l. anthranilic acid-containing bath at a bath ratio of 30 at 100 C. The fastness of the dyed material was found to be 5th class on the J IS Standards.

Example 13 To polypropylene resin pellet having an average molecular weight of 150,000, was added 5% by weight tetramethylene aminotriazole-tetramethylene triazole condensation polymer (n: 10), obtained by the condensation polymerisation of adipic acid dihydrazide and hydrazine hydrate. The resulting mixture was spun in the same manner as described in the preceding examples, and the spun yarn was processed by crimping and then out to 3 in. staples. The staple fibre thus produced was immersed in a solution containing 10 g./l. salicyclic acid at 100 C. for 30 minutes, and was then dyed to a deep purple color with 5% Benzyl Violet 3B (C.I. Acid Violet 17, 42,650) at a bath ratio of 50, at 100 C. The dyed material passed the HS Standards, 5th class, in its resistance to both abrasion and laundering.

Example 14 T o isotactic polypropylene resin having an average molecular weight of 150,000 was added 5% by weight a copolymer of poly(octamethylene-44auryltriazole) and poly(octamethylene-4-a1ninotriazole) (11:5) obtained by reacting a sebacic acid dihydrazide condensation polymer with laurylamine and 80% hydrazine hydrate and further treating the resultant polymer with acetic hydrazide. The resulting mixture was subjected to melt spinning to produce yarn comprising multifilaments of 90 deniers/ 15 filaments. The yarn so produced was dyed to a brilliant blue color by using a dyeing bath of 3% Xylene Brilliant Cyanine 6B (C.I. Acid Blue 83, 42,660) containing salicylic acid at a concentration of 10 g./l. at a bath ratio of 50 and a temperature of 100 C. for one hour. The dyed material had good resistance to both abrasion and laundering, high enough to pass the HS Standards, 5th class.

Example 15 To low pressure polyethylene resin having an average molecular weight of 150,000 was added 5% by weight a copolymer of poly(octamethylene-4-stearyltriazole) and poly(octamethylene-4-amino triazole) (11:7), obtained by reacting seb-acic acid dihydrazide condensation polymer with stearylamine and 80% hydrazine hydrate, and further treating the result polymer with lauric acid hydrazide. The resulting mixture was subjected to melting spinning to produce yarn comprising multifilaments of 90 deniers/ 15 filaments. The yarn was dyed to a deep purple color with 3% Benzyl Violet 3B (C.I. Acid Violet 17,

O 0 42,650) in a 10 g./l. salicylic acid-containing dyeing bath (the bath ratio was 30 and the temperature 100 C.). The dyed material passed the I IS Standards, 5th class, in its resistance to abrasion and laundering.

Example 16 To polypropylene resin powder having an average molecular weight of 100,000, was added 3% by weight poly(cyclohexylene-4-tertiary butyl triazol-cyclohexylene- 4-amino-triazole) (11:4), obtained by reacting a 1,4- cyclohexyl dicarboxylic acid dihydrazide condensation polymer with tertiary butylamine and further treating the resultant polymer with nicotinic acid hydrazide. The resulting mixture was subjected to melt spinning to produce yarn comprising multifilaments of 210 deniers/ 15 filaments. The yarn was dyed to a beautiful deep purple color with 3% Benzyl Violet 3B (C.I. Acid Violet 17, 42,650) in a 10 g./l. salicylic acid-containing dyeing bath (the bath ratio was 50 and the temperature 100 C.). The fastness of the dyed material was found to be 5th lass on the I IS Standards.

Example 17 To low pressure polyethylene pellet having an average molecular weight of 150,000 was added 5% by weight poly(octamethylene 4 oleyl triazole-octamethylene 4- aminotriazole) (11:8), obtained by reacting a sebacic acid dihydrazide condensation polymer with oleylamine and hydrazine hydrate and further treating the resultant polymer with acetamide. The resulting mixture was subjected to melt spinning to produce yarn of 10 denier monofilaments. The yarn was treated with a solution of 10 g./l. benzoic acid at 100 C. for one hour and was then dyed to a beautiful red color with 3% Rose Bengale DY (C.I. Acid Red 94, 45,440) at a bath ratio of 30 for one hour. The fastness was found to be JIS Standards, 5th class.

When aromatic carboxylic acids are employed in accordance with the principle of this invention, the exhaustion of dye from the dye bath as provided by the above-described examples is greater than By contrast when sulfuric acid or acetic acid is used instead of the aromatic carboxylic acids to obtain a solution with a pH of from 3.5 to 3, the exhaustion of dye from the dye bath is smaller than 70%,

The degree of condensation n is determined by the osmotic pressure method with the use of a benzyl-alcohol (for a low molecular weight polymer) or a m-cresol (for a high molecular weight polymer) solution or by the end group analysis with the use of K10 What is claimed is:

1. In a process for dyeing shaped articles produced from polyolefin material selected from the group consisting of polyethylene, polypropylene and polybutenes, the improvement comprising improving the dyeability of the polyolefin article by reacting the article with a monocyclic aromatic carboxylic acid which contains one benzene ring, said polyolefins having been modified by the addition thereto 1 to 20% by weight of a material having a melting point between and 300 C. and having the following general formula wherein R and R are members selected from the group consisting of alkylene, phenylene, cycloalkylene, pyridyl and naphthyl, the alkylene being represented by the formula (CH wherein n is a number between 2 and 10; X and X are members selected from the group consisting of hydrogen, alkyl, alkenyl, phenyl, naphthyl, amino, benzalamino, formalamino, acetamino, carbamylamino, pyrrolyl and pyridyl radicals, the alkyl radical having from 1 to 18 carbon atoms and being linear or branched, the alkenyl radical having from 2 to 18 carbon atoms; Z and Z are selected from the group consisting of carboxyl and hydrazide radicals; and n is a number greater than one.

2. A process as claimed in claim 1 comprising dyeing said article in a dye bath including said acid.

3. A process as claimed in claim 1 comprising treating the shaped article with an aromatic carboxylic acid at a temperature of from normal room temperature to 150 C.

4. A process as claimed in claim 1, wherein the aromatic carboxylic acid is used in an amount of more than 1% based on the weight of the shaped article to be treated.

5. A process as claimed in claim 1, wherein the said aromatic carboxylic acid which contains one benzene ring is selected from the group consisting of benzoic acid, cinnamic acid, phthalic acid and benzoic acids substituted with at least one of the group consisting of methyl, ethyl, halogeno, nitro, nitroso, amino, hydroxy, and sulfo group.

References Cited by the Examiner UNITED STATES PATENTS 2,512,629 6/1950 Fisher et al 260-78.4 X 2,628,152 2/1953 Meuneir et al 8-55 3,107,228 11/1963 Cappuccio et a1 8-55 X 3,115,478 12/1963 Natta et a1. 260-455 3,137,989 6/1964 Fior et al. 260-897 X 3,184,281 5/1965 Tsunoda et al. 8-4

NORMAN G. TORCHIN, Primary Examiner. D. LEVY, Assistant Examiner. 

1. IN A PROCESS FOR DYEING SHAPED ATICLES PRODUCED FROM POLYOLEFIN MATERIAL SELECTED FROM THE GROUP CONSISTING OF POLYETHYLENE, POLYPROPYLENE AND POLYBUTENES, THE IMPROVEMENT COMPRISING IMPROVING THE DYEABILITY OF THE POLYOLEFIN ARTICLE BY REACTING THE ARTICLE WITH A MONOCYCLIC AROMATIC CARBOXYLIC ACID WHICH CONTAINS ON BENZENE RING, SAID POLYOLEFINS HAVING BEEN MODIFIED BY THE ADDITION THERETO 1 TO 20% BY WEIGHT OF A MATERIAL HAVING A MELTING POINT BETWEEN 100* AND 300*C. AND HAVING THE FOLLOWING GENERAL FORMULA 